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Publication numberUS2680096 A
Publication typeGrant
Publication dateJun 1, 1954
Filing dateFeb 12, 1951
Priority dateFeb 12, 1951
Publication numberUS 2680096 A, US 2680096A, US-A-2680096, US2680096 A, US2680096A
InventorsNoel P Shiells, James H Walker
Original AssigneeCalifornia Research Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for preparing sulfurized polyvalent metal phenates
US 2680096 A
Abstract  available in
Images(4)
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Claims  available in
Description  (OCR text may contain errors)

Patented June 1, 1954 PROCESS FOR PREPARING SULFURIZED POLYVALENT METAL PHENATES James H. Walker and Noel P. Shiells, Richmond,

Califl, assignors to California, Research Corporation, San Francisco, Calif., a corporation of Delaware No Drawing. Application February 12, 1951, Serial No. 210,622

6 Claims. 1

This invention pertains to a new method of manufacturing calcium phenates containing sulfur; that is, sulfurized calcium phenates.

Sulfurized calcium alkyl phenates are used as compounding agents in lubricating oils to inhibit corrosion, piston ring sticking and gum formation in internal combustion engines resulting from oxidation of the lubricating oil and polymerization of the engine fuel residues.

.Normal and basic sulfurized calcium phenates are excellent lubricating oil additives. Numerous attempts have been made in recent years to prepare oil-soluble sulfurized calcium phenates having the detergent characteristics of the phenates, and, in addition, the property of neutralizing larger amounts of acidic bodies than possible heretofore with the presently-available normal sulfurized calcium alkyl phenates. The sulfurized calcium alkyl phenates which are disclosed herein as having greater neutralizing properties than those heretofore available will hereinafter be known as basic sulfurized calcium phenates.

As used herein, normal sulfurized calcium phenates refer to sulfurized calcium phenates wherein the ratio of calcium to the phenol nucleus is about 1:2, such as R Ca wherein R represents alkyl substituent radicals on a benzene ring.

As used herein, the term basic sulfurized calcium phenates refers to sulfurized calcium phenates wherein the ratio of calcium metal to phenol is greater that that ofthe normal sulfurized calcium phenates.

It is a particular advantage of this invention that basic sulfurized calcium phenates (e. g., basic sulfurized calcium hexadecyl phenate) having metal contents up to and greater than 100% in excess of the metal present in the corresponding sulfurized normal calcium phenates can be prepared. I-Ieretofore, the attempted preparation of basic sulfurized calcium phenates has resulted in the formation of a gel-like substance not filterable.

Basic sulfurized metal phenates are particularly useful when incorporated in lubricating oil compositions for diesel engines.

Numerous difficulties which have been encountered heretofore in the preparation of sulfurlzed calcium alkyl phenates include (1) the difficulty of filtering the reaction mixture to remove the unreacted calcium oxide or hydroxide, (2) the necessity of using a two-step process, etc. According to the process of the present invention, these difiiculties and others are overcome; for example, less time is consumed in the preparation of sulfurized calcium alkyl phenates.

It is a primary object of this invention to set .forth a method of preparing sulfurized calcium phenates.

It is an object of this invention to provide a method of producing basic sulfurized calcium phenates having metal contents up to and greater than in excess of that present in the corresponding sulfurized normal calcium phenates.

These and other objects of this invention will be apparent from the ensuing description and the appended claims.

It has been discovered that oil-soluble sulfurized calcium phenates, that is, oil-soluble normal sulfurized calcium phenates and basic sulfurized calcium phenates, can be prepared by the reaction of phenols with calcium oxides or hydroxides in the presence of glycols and sulfur.

As used herein, the term phenol means phenol and derivatives of phenol; similarly, the term calcium phenate means the calcium salt of phenol and derivatives of phenol.

The calcium phenates which are to be reacted with sulfur to form the sulfurized calcium phenate are of the formula:

[ (R) EAO] 20a bonaceous) radical is meant those radicals whichare composed mainly of hydrogen and carbon, and include such radicals which contain, in addition, minor amounts of substituents, such as chlorine, bromine, oxygen, sulfur, nitrogen, etc., which do not substantially afiect their hydrocarbon character.

Examples of suitable hydrocarbonaceous radicals include alkyl radicals such as butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl, triacontyl radicals; radicals derived from petroleum hydrocarbons, such as white oil, wax, olefin polymers (e. g., polypropylene and polybutylene), etc.; aryl radicals such as phenyl, naphthyl, etc.

aralkyl radicals such as phenyloctyl, phenyldecyl, phenyloctadecyl, etc.; alkaryl radicals such as amylphenyl, cetylphenyl, etc.; and cyclic nonbenzenoid radicals, such as cyclohexyl, bornyl, etc.

Examples of calcium phenates include the calcium salts of octyl phenol, decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol, triacontyl phenol, etc.

The glycols used as the solvent to prepare the sulfurized calcium phenates of this invention may contain up to 6 carbon atoms. Suitable plycols include: ethylene glycol, propylene glycol, butane diol-2,3; pentane diol-2,3; and Z-methyl butane diol-3,4. Because of the higher yield of product obtained, ethylene glycol is the preferred solvent.

The basic sulfurized calcium phenates may be prepared from normal calcium alkyl phenates or from phenols. When phenols are used as starting materials, the phenols are treated with calcium oxide or hydroxide to form the desired normal calcium phenates, which phenates are then treated further with calcium oxide or hydroxide and sulfur to form the sulfurized basic calcium phenate. On the other hand, the phenols may be treated with calcium oxides or hydroxides and sulfur in amounts suiiicient to form the sulfurized basic calcium phenates directly without the initial formation and separation of the normal calcium phenates.

According to the process of this invention, in the preparation of normal or basic sulfurized calcium phenates, it is essential that elemental sulfur be present along with the calcium oxide or hydroxide. That is, in the preparation of a sulfurized normal calcium alkyl phenate, for example, it is essential that the aikyl phenol, calcium oxide or hydroxide, elemental sulfur and glycol be blended together for the reaction. Similarly, in the preparation of a sulfurized basic calcium alkyl phenate, for example, it is necessary to mix together the alkyl phenol, calcium oxide or hydroxide, elemental sulfur and glycol.

The amount of elemental sulfur present in the reaction mixture can vary from 10 mol per cent to 200 mol per cent (based on the calcium). It is preferred to use from 50 to 125 mol per cent (based on calcium) As noted hereinabove, the amount of calcium oxide or hydroxide used is that amount which will be sufficient to give the basic sulfurized calcium phenate an amount of calcium u to and greater than 100% more calcium than that which is present in the normal calcium phenates. The amount of calcium oxides or hydroxides used in the reaction depends somewhat on the amount of calcium desired in the product in excess of that of the normal phenates, and, as noted hereinbelow, also depends on the weight ratio of glycol to calcium oxide or hydroxide used. Normally, in the preparation of a basic sulfurized calcium phenate, a slight excess (e. g., 10 mol per cent excess) of calcium oxide or hydroxide is used in the reaction over that desired in the final basic phenate product.

The amount of the glycol used will depend in part upon the nature of the glycol itself which is used, and, as noted above, on the amount of calcium oxide or hydroxide used. In general, the use of low molecular weight glycols (e. g., ethylene glycol) results in obtaining a higher yield of the basic phenate than does the use of higher molecular weight glycols (e. g., propylene glycol) when both are used in the same amounts by 1* positions.

Weight. The amount of glycol used is also governed by the solubility of the acidic substance (the phenols or the calcium phenates) and the calcium oxide and hydroxide in the glycol.

It is preferred in practicing this invention to select a glycol in which phenols, normal phenates and calcium oxides and hydroxides have the greatest solubility.

A sufiicient amount of glycol is employed to bring the reactant into eflicient contact for substantial reaction in a reasonably short time. That is, the amount of glycol used is sufficient to dissolve a portion of each of the reactants and to cause substantial contact between said reactants. For this purpose, it is beneficial to use certain ratios by weight of the glycol to the calcium oxide or hydroxide, which ratio may be from about 50 to 1 to about 1 to 1; 25 to 1 to about 2 to 1 being preferred.

The temperatures at which the reactants of this invention will react in the presence of glycols are dependent to a large extent on the nature of the acidic substance (i. e., the phenols or the neutral calcium phenates), the calcium oxide or hydroxide and the glycol.

Although the reaction may take place at atmospheric pressure, it is desirable that this process take place at reduced pressures. Thus, it is preferred to use the minimum temperatures at which the reaction will take place at reduced pressures, the reduced pressure and the temperature to be guided by the glycol used. It is preferred to use a pressure substantially less than atmospheric pressure; that is, it is preferred to use a reduced pressure in order that the glycol may be distilled off from the mixture at a temperature less than 400 F. Thus, the maximum temperature of the reaction may be about 400 F. with a minimum temperature of about 200 F.

In the reaction process set forth in this invention, it is preferred to incorporate lubricating oil in the mixture because the resulting lubricating oil solution is then readily usable as a base for the preparation of useful lubricating oil com- Also,the presence of the lubricating oil decreases the viscosity of the mixture and facilitates the handling of the reaction mixture.

Lubricating oils which may be used for this purpose include a wide variety of lubricating oils such as naphthenic base, paraffin base, and mixed base mineral oils, other hydrocarbon lubricants, e. g., lubricating oils derived from coal products and synthetic oils, e. g., allrylene polymers (such as polymers of propylene, butylene, etc., and mixtures thereof), alkylene oxide type polymers, dicarboxylic acid esters and liquid esters of acids of phosphorus. Synthetic oils of the alkylene oxide type polymer which may be used include those exemplified by alkylene oxide polymers (e. g., propylene oxide polymers) and derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxides (e. g., propylene oxide) in the presence of water or alcohols, e. g., ethyl alcohol, and esters of alkylene oxide type polymers, e. g., acetylated propylene oxide polymers prepared by acetylating the propylene oxide polymers containing hydroxyl groups.

The following examples, with the exception of Example 1, illustrate the preparation of sulfurized calcium phenates according to the present invention. Example I illustrates the preparation of an alkyl phenol, Examples II to V, inclusive, illustrate the preparation of basic sulfurized calcium phenates, and Examples VI to VIII, inclusiye, i lustrate th preparati n of n mal sul urizecl calcium phenate. The molecular weights of the alkyl phenols used in the following examples ranged from 285 to 300.

Example I A mixture consisting of 300 parts by weight of phenol, 555 parts by weight of olefin polymers having average molecular weights of 170, and 45 parts by weight of acid-treated clay was heated at 300 F. for a period of 12 hours, after which time the mixture was filtered. The remaining reaction was heated to 530 F. to remove unreacted phenol, olefin polymers and low molecular weight phenols. The resulting product was used in the preparation of normal sulfurized calcium alkyl phenates and basic sulfurized calcium alkyl phenates.

Example II mercury. After the water of reaction had been distilled off, the pressure was reduced to 60 mm. of mercury and the temperature raised to 380 F.. at which temperature and pressure the ethylene glycol was removed. During the period when the ethylene glycol. was being removed, 400 parts by weight of petroleum lubricating oil were added. .When all of the ethylene glycol had been removed, the mixture was cooled and 200 parts by weight of a petroleum thinner were added and the mixture was filtered. lhe filtrate was heated at reduced pressure to remove the petroleum thinner. The final lubricating oil composition contained 2.85 sulfur and 5.63% calcium; the basic sulfurized calcium alkyl phenate containing 92% more calcium than that present in the corresponding normal calcium alkylphenate.

Example III A mixture of 400 parts by weight of an alkyl .phenol having a boiling range of 560 to 700 F. i

and 33 parts by weight of sulfur was heated to 200 F. To this mixture was added a slurry of .81 parts by weight of calcium hydroxide, 200 parts by weight of ethylene glycol and 200 parts by weight of a petroleum lubricating oil having a viscosity of 49.5 S. S. U. at 210 F. At an absolute pressure of 16 min. of mercury, the mixture was heated to distill off the water of reaction and the ethylene glycol. During this time, an additional .200 parts by Weight of petroleum lubricating oil was added. The whole mixture was heated to 380 F. at a pressure of 16' mm. of mercury in order to remove the ethylene glycol. After the product had been filtered, the reaction mixture contained 2.08% sulfur and 3.81% calcium. The basic sulfurized calcium alkyl phenate contained 50% more calcium than that resent in the corresponding normal sulfurized calcium alkyl phenate.

Example IV A mixture of 100 parts by weight of an alkyl phenol having a hydroxyl number of 150, 50 parts by weight of ethylene glycol, 20 parts by weight of calcium hydroxide, 8 parts by weight of elemental sulfur, and 200 parts by weight of a, petroleum lubricating oil was heated for one hour at a temperature of 380 to 400 F. and an absolute .pressure of 50 to 60 mm. of mercury. This reaction mixture was filtered hot. The resulting :to remove the ethylene glycol.

6 petroleum lubricating oil composition contained 1.43% sulfur and 2.67% calcium. The basic sulzfurized calcium alkyl phenate contained 60% more metal than that present in the normalsulfurized calcium alkyl phenate.

Example V pressure (50 to 60 mm. of mercury-abso1ute pressure) to 380 at which temperature and pressure the reaction mixture was held for one hour with stirring. The reaction mixture was filtered at 380 F., and the reaction product con- .tained 1.30% sulfur and 2.70% calcium. The basic sulfurized calcium alkyl phenate contained 75% more calcium than that present in the normal sulfurized calcium alkyl henate.

Example V I A. mixture of parts by weight of ethylene glycol, 19.3 parts by weight of elemental sulfur was heated with agitation to 250 F. To this mixture was slowly added a slurry consisting of 400 parts by weight of an alkyl phenol having a hydroxyl number of and 48 parts by weight of calcium hydroxide. This whole mixture was heated at 300 F. for 1 /2 hours, after which the pressure was gradually reduced to 40 mm. of mercury and the temperature raised to 360 F. When approximately of the ethylene glycol had been removed, 257 parts by weight of a mineral lubricating oil were added. The final of ethylene. glycol was then removed by heating to 350 F. at

A mixture of 600 parts by weight of an alkyl.

phenol having a hydroxyl number of 160 and 31 grams of sulfur was heated to 300 F. To this mixture was added a slurry of 65 parts by weight of calcium hydroxide and 200 parts by weight of ethylene glycol, maintaining the temperature at 300 F. The absolute pressure of the reaction vessel was reduced to 40 mm. of mercury. The temperature was gradually raised to 360 F., during which time about /3 of. the ethylene glycol was removed. When about of the ethylene glycol had been removed by distillation, about 257 parts by weight of lubricating oil were added, and the remaining of ethylene glycol was removed at a temperature of 360 F. and an absolute pressure of 40 mm. of mercury. After the reaction mixture had been filtered, the resulting lubricating oil solution contained 3.16% calcium and 2.28% sulfur.

Example VIII A mixture of 300 parts by weight of an alkyl phenol having a hydroxyl number of 155, 40 parts by weight of calcium hydroxide, 19 parts by weight of sulfur, 50 parts by weight of ethylene glycol, and 200 parts by weight of a petroleum lubricating oil was slowly heated up to a tempera ture of 375 F. at an absolute pressure of 60 mm. of mercury. The temperature of 375 F. was

maintained for 3 hours to remove all of the ethylene glycol; after which time the reaction mixture was filtered. The lubricating oil solution of normal sulfurized calcium alkyl phenate contained 3.83% calcium and 1.67% sulfur.

The following Example IX further illustrates the preparation of sulfurized calcium alkyl phenates according to the process of this invention.

Example IX A mixture of 70 parts by Weight of an alkyl phenol having a hydroxyl number of 168, '70 parts by weight of ethylene glycol and 6 parts by weight of calcium oxide was heated to 150 F. until all of the calcium oxide was dissolved. To this mixture was added 70 parts by weight of a light mineral lubricating oil and 4 parts by weight of sulfur. The temperature was slightly raised to 400 F. at a slightly reduced pressure. After all of the ethylene glycol had been removed the temperature of the reaction mixture Was kept at 350 F. for approximately 30 minutes. After filtration, the reaction mixture contained 4.10% calcium and 2.08% sulfur.

We claim:

1. A method of stably incorporating sulfur and calcium into phenate materials to form highly oil-soluble sulfurized calcium phenates, which comprises bringing together into admixture: a phenol having up to 30 carbon atoms in any alkyl substituents on the ring, a calcium base selected from the group consisting of oxide and hydroxide and in an amount sufficient to form a sulfurized calcium alkyl phenate having a calcium metal-phenol mol ratio of at least 0.5, elemental sulfur in an amount of -200 mol per cent based on calcium, and a glycol containing less than 6 carbon atoms, the ratio of said glycol to calcium base being from 1 to about 50, and heating the mixture sufdoiently to produce a sulfurized calcium alkyl phenate and toremove said glycol.

2. A method of stably incorporating sulfur and calcium into phenate materials to form highly oil-soluble sulfurized calcium phenates, which comprises bringing together into admixture: an alkyl phenol containing at least one alkyl radical of 4 to 30 carbon atoms, a calcium base selected from the group consisting of oxide and hydroxide and in an amount sufiicient to form a sulfurized calcium alkyl phenate having a calcium metalphenol mol ratio of at least 0.5, elemental sulfur in an amount of 10-200 mol per cent based on calcium, and a glycol containing less than 6 carbon atoms, the ratio of said glycol to calcium base being from 1 to about 50, then heating under conditions of temperature and pressure to remove water of reaction, and thereafter by distillation removing said glycol.

3. The process of claim 2 wherein the temperature is maintained below 400 F.

4. The process of claim 3 wherein the removal 8 of water is at an absolute pressure substantially less than atmospheric.

5. A method of stably incorporating sulfur and calcium into phenate materials to form highly oil-soluble calcium phenates, which comprises bringing together into admixture: an alkyl phenol containing at least one alkyl radical of 4 to 30 carbon atoms, a calcium base selected from the group consisting of oxide and hydroxide and in an amount sufficient to form a suliurized calcium phenate having a calcium metal-phenol mol ratio of at least 0.5, elemental sulfur in an amount of 10-200 mol per cent based on calcium and ethylene glycol in a ratio to said calcium base of from one to about 50, reducing the pressure on the resulting reaction mixture to an absolute pressure ranging from 350-450 mm. of mercury, slowly heating the reaction mixture to a temperature ranging from 240-300 F. for a time sumcient to remove the water of reaction, reducing the pressure to an absolute pressure of less than 15 mm. of mercury, slowly heating the reaction mixture to a temperature ranging from 325-400 F. for a time sufficient to remove more than 50% of the ethylene glycol by distillation; adding a lubricating oil as a diluent, heating the resulting mixture to an absolute pressure less than 150 of mercury at a temperature ranging from 325-400 F. until the remaining ethylene glycol has been substantially removed by distillation, and filtering the remaining reaction' mixture.

6. A method for stably incorporating sulfur and calcium into phenate materials to form highly oil-soluble suliurized calcium phenates, which comprises intermixing: (l) a phenate material selected from the group consisting of phenols having up to 30 carbon atoms in any alkyl substituents on the ring and normal calcium salts of said phenols, (2) a calcium base selected from the group consisting of oxide and hydroxide and in an amount at least sufficient to form a sulfurized calcium alkyl phenate having a calcium metal-phenol mol ratio of at least 0.5 and up to mol per cent in excess over the calcium present in normal calcium phenate, (3) elemental sulfur in an amount of 10-200 mol per cent based on calcium, and (4) a glycol containing less than 6 carbon atoms, the ratio of said glycol to calcium base being from one to about 50, and heating the resulting mixture at a temperature less than 400 F. and at an absolute pressure sub stantially less than atmospheric for a time suincient to produce a sulfurized calcium alkyl phenate and to remove said glycol.

References Cited in the file Of this patent UNITED STATES PATENTS Number Name Date 2,406,564 Rogers et a1 Aug. 2'7, 1946 2,409,687 Rogers et al Oct. 22, 1946

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2406564 *May 10, 1943Aug 27, 1946Standard Oil Dev CoCompounded lubricating oil
US2409687 *Aug 1, 1944Oct 22, 1946Standard Oil Dev CoSulfur and metal containing compound
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2975132 *Jun 18, 1956Mar 14, 1961California Research CorpEmulsifiable lubricant compositions
US2989466 *Oct 6, 1959Jun 20, 1961California Research CorpOxyalkylated-carbonated phenates in lubricating oils
US3036971 *Dec 24, 1958May 29, 1962Socony Mobil Oil Co IncLubricating oils containing carbonated basic sulfurized calcium phenates
US3178368 *May 15, 1962Apr 13, 1965California Research CorpProcess for basic sulfurized metal phenates
US3194761 *Mar 3, 1961Jul 13, 1965Distillers Co Yeast LtdPreparation of overbased sulphurized calcium alkylphenate lubricant additives
US3410798 *May 23, 1967Nov 12, 1968Lubrizol CorpBasic, sulfurized phenates and salicylates and method for their preparation
US3424679 *Aug 15, 1966Jan 28, 1969Chevron ResNonvicinal glycols in overbased phenate preparation
US3464970 *Mar 13, 1967Sep 2, 1969Maruzen Oil Co LtdProcess for preparing over-based sulfurized calcium phenates
US3528917 *May 22, 1967Sep 15, 1970Texaco IncSulfurized calcium alkylphenolate lubricant compositions
US3549534 *Sep 5, 1969Dec 22, 1970Texaco Development CorpSulfurized calcium alkylphenolate lubricant compositions and method of manufacture
US4412927 *Feb 19, 1982Nov 1, 1983Orogil CorporationProcess for the preparation of superalkalinized metallic detergent-dispersants for lubricating oils and products obtained therefrom
US4588416 *Sep 20, 1985May 13, 1986Ethyl CorporationFuel compositions
US4608184 *Jul 12, 1985Aug 26, 1986Amoco CorporationPhenate process and composition improvement
US4710308 *Apr 18, 1984Dec 1, 1987Amoco CorporationProcess for preparing overbased sulfurized phenates
US4973411 *Sep 15, 1989Nov 27, 1990Texaco Inc.Process for the preparation of sulfurized overbased phenate detergents
US5169545 *Aug 30, 1991Dec 8, 1992Mobil Oil CorporationMetal phenate sulfides
US5223163 *Mar 18, 1992Jun 29, 1993Mobil Oil CorporationMetal phenates
US5529705 *Mar 17, 1995Jun 25, 1996Chevron Chemical CompanyMethods for preparing normal and overbased phenates
US5759966 *Oct 1, 1996Jun 2, 1998Chevron Chemical CompanyHigh overbased metal sulfurized alkyphenates
US7943796Jul 31, 2008May 17, 2011Chevron Oronise Company LLCLubricating oil additive and lubricating oil composition containing same
US8183192Feb 3, 2010May 22, 2012Chevron Oronite Company LlcLubricating oil additive and lubricating oil composition containing same
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US8796192Oct 29, 2010Aug 5, 2014Chevron Oronite Company LlcNatural gas engine lubricating oil compositions
US8841243Mar 31, 2010Sep 23, 2014Chevron Oronite Company LlcNatural gas engine lubricating oil compositions
US8969273Feb 18, 2009Mar 3, 2015Chevron Oronite Company LlcLubricating oil compositions
US9353327Dec 12, 2012May 31, 2016Chevron Oronite Company LlcDiesel engine oils
US9434906Mar 25, 2013Sep 6, 2016Chevron Oronite Company, LlcMarine diesel engine lubricating oil compositions
US20100029527 *Jul 31, 2008Feb 4, 2010Chevron Oronite Company LlcLubricating oil additive and lubricating oil composition containing same
US20110190185 *Feb 3, 2010Aug 4, 2011Chevron Oronite Company LlcLubricating oil additive and lubricating oil composition containing same
USRE29661 *Jul 5, 1977Jun 6, 1978Chevron Research CompanySulfurized metal phenates
DE1144732B *Apr 12, 1960Mar 7, 1963Basf AgVerfahren zur Herstellung von Schmieroelzusatzstoffen
DE2224073A1 *May 17, 1972Nov 30, 1972 Title not available
DE2620539A1 *May 10, 1976Jul 7, 1977Liquichimica Robassomero SpaVerfahren zur herstellung von schmieroelzusaetzen
DE3244638A1 *Dec 2, 1982Jun 9, 1983Agip PetroliVerfahren zur herstellung von superbasischen detergentien
EP3072948A1Mar 9, 2016Sep 28, 2016Chevron Japan Ltd.Lubricating oil compositions for construction machines
WO2013059173A1Oct 16, 2012Apr 25, 2013The Lubrizol CorporationBridged alkylphenol compounds
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Classifications
U.S. Classification508/574, 568/75
International ClassificationC10M159/22, C07C39/235
Cooperative ClassificationC10M2219/02, C10M2205/024, C10M2219/088, C10M2205/026, C10M2209/108, C10M2219/089, C10M2209/105, C10M2207/34, C10M2207/282, C10M2223/042, C10M159/22, C10M2219/087, C10M2209/109, C10M2209/103, C10M2223/04
European ClassificationC10M159/22